Low VOC, fluorocompound-containing one-component and two-component coating compositions for slippery coatings

ABSTRACT

This invention relates to one-component and two-component heat-curable or moisture-curable coating compositions, and processes for their use in providing a slippery coating on a substrate utilizing a polyisocyanate-based low VOC coating composition, employing a fluoro-containing active hydrogen-containing compound, and which is suitably rapidly hardened under the influence of heat or moisture.

FIELD OF THE INVENTION

This invention relates generally to one-component and two-componentheat-curable or moisture-curable coating compositions for providing aslippery coating on a substrate, and, more specifically to a process forcoating substrates with a coating composition containing a low or nilconcentration of volatile organics (so-called "low VOC", containing, atmost, a low amount of organic solvent) and which is suitably rapidlyhardened under the influence of heat or moisture.

BACKGROUND OF THE INVENTION

The use of fluorine-containing compounds in preparing coatings having aslippery outer surface is known in the art. By way of illustration,European Patent Application publication No. 480,089, published on Apr.15, 1992 discloses the reaction of isophorone diisocyanate ("IPDI") witha fluorine-containing monoalcohol ("monol") in order to prepare afluoro-modified urethane for use as a resin modifier by grafting onto afluoroolefin-vinyl ether copolymer resin. The modified resin wassubsequently used in accordance with the disclosures of the '089publication to modify a coating composition comprising the modifiedresin having a 50% solids content, and coated substrates were preparedand their physical properties measured. The '089 publication alsodiscloses, at page 12 thereof, a "wish-list" of conventionalfilm-forming resins suitable for use in combination with the modifiedresin in coating compositions, including polyurethane resins.

The use of moisture-curable one-component and two-componentisocyanate-based coating compositions in the production of coatings forsubstrates is also known in the art. As an illustration of aone-component system, U.S. Pat. No. 4,456,658 discloses a process forcoating polyvinyl chloride sheet products with a moisture-curable, clearcoating comprising a binder which consists essentially of at least onepolyisocyanate which is liquid at room temperature. The polyisocyanatebinder is further characterized at column 2, lines 12-17 of the '658patent as being in particular polyisocyanates containing biuret orisocyanurate groups and optionally uretidione groups and having anaverage isocyanate functionality above 2, preferably from about 2.5 to6. Unfortunately, the '658 patent is limited to coating polyvinylchloride sheet products, which represents a narrow market niche ascompared to the wide variety of substrates in the marketplace that couldbenefit from a suitable one-component coating. The coating compositionsof the examples of the '658 patent also have the disadvantage of slowdrying times when cured with atmospheric moisture at room temperature.

As an additional illustration, U.S. Pat. No. 4,292,350 discloses aprocess of coating substrates comprising applying to the substrate amoisture-curable, solvent-free or low solvent lacquer compositioncontaining as a binder an isocyanate mixture. The isocyanate mixturedescribed in the '350 patent is a mixture of (a) an organicpolyisocyanate having an average isocyanate functionality of greaterthan 2 which contains biuret, urethane and/or isocyanurate groups andhas an isocyanate content of from about 13 to 30% by weight, and (b) atleast one monoisocyanate having a defined structure. The monoisocyanateis further described at column 3, lines 18-22 of the '350 patent asbeing suitably prepared by reacting excess quantities of a diisocyanatewith a hydrocarbon-containing hydroxyl compound, followed by removal ofunreacted excess diisocyanate by distillation using, for example, a thinlayer evaporator. The process of this patent is more cumbersome thanmight be desired, particularly in regard to the need for the isocyanatemixture and the need for removal of excess diisocyanate from theprepared monoisocyanate component.

Conventional methods for the heat-curing of monomeric diisocyanates havefrequently posed toxicity concerns that are typically associated withemployee exposure by the end user to volatile monomeric diisocyanates.

Recent efforts have been made to overcome these toxicity concerns;however, other problems tend to occur. By way of illustration, U.S. Pat.No. 5,144,031 discloses both heat-crosslinkable, one-componentblocked-isocyanate compositions and two-component coating compositionswhich are said to harden at room temperature or at a slightly elevatedtemperature. The coating compositions of the '031 patent containisocyanurate group-containing polyisocyanates produced by the steps of:(a) partially trimerizing the isocyanate groups of a cycloaliphaticdiisocyanate in the presence of a trimerization catalyst and optionallyin the presence of an inert solvent, (b) terminating the trimerizationreaction at the desired degree of trimerization, (c) removing unreactedstarting diisocyanate and any other volatile constituents, and (d) priorto step (c), adding 1 to 30 % by weight of a monohydric alcohol being anester alcohol, based upon the weight of the diisocyanate. Unfortunately,this process is more complicated than might be desired, particularlywith the requirement for the step (c) removal of unreacted startingdiisocyanate after addition of the monohydric alcohol. In addition, thepresence of the ester alcohol necessitates that a urethanizationreaction takes place at the site of the ester alcohol on the prepolymer,in addition to the trimerization reaction that takes place with respectto the isocyanate moieties, rendering a more complex reaction sequencethan might be desired.

Recently, new processes for providing low VOC one-component andtwo-component heat or moisture curable urethane coatings based onorganic polyisocyanates, and advantageously employing dimers, trimers,or biurets of aliphatic diisocyanates, have been disclosed, for example,in commonly-assigned, co-pending U.S. application Ser. Nos. 08/065,005(filed on May 24, 1993 and claiming low VOC, 1-K moisture curablecoating compositions), 08/064,996 (filed on May 24, 1993 and claiminglow VOC, 2-K moisture curable coating compositions), and 08/065,009(filed on May 24, 1993 and claiming low VOC, 1-K and 2-K heat curablecoating compositions). The processes disclosed in these copendingapplications, although useful for coating a wide variety of substrates,not limited to the polyvinyl chloride substrate of the '658 patent andnot employing the isocyanate mixture of the '350 patent, have thedisadvantage of not always providing as "slippery" a coating asotherwise might be desired in use, for example, as an automotivetop-coat, clear-finish coating. Accordingly, new coating compositionsand processes providing the desired slipperiness characteristics for thecoating's outer surface, without compromising good substrate adhesioncharacteristics between the coating and the underlying substrate, wouldbe highly desired by the coatings manufacturing community. The presentinvention provides one solution to this industry need. The presentinvention also provides a solution to the toxicity problem that can beassociated with monomeric diisocyanates by employing a low toxicitycoating composition that is also low in VOC.

SUMMARY OF THE INVENTION

In one aspect, the present invention relates to a low volatile-organics,one-component, heat curable coating composition having a viscosity asmeasured by ZAHN cup 2 of less than about 200 seconds and consistingessentially of at least one blocked polyisocyanate, afluorine-containing active hydrogen-containing compound alone or incombination with a fluorine-free active hydrogen-containing compound, asolvent in an amount of between 0% and 45% by weight based upon theamount of said polyisocyanate in said composition, and a trimerizationcatalyst, said composition being essentially free of any mono- anddi-isocyanate monomers, and said composition being heat curable uponexposure to heat.

In another aspect, the present invention relates to a lowvolatile-organics, two-component, heat curable coating compositionhaving a viscosity as measured by ZAHN cup 2 of less than about 200seconds and consisting essentially of at least one polyisocyanate, afluorine-containing active hydrogen-containing compound alone or incombination with a fluorine-free active hydrogen-containing compound, asolvent in an amount of between 0% and 45% by weight based upon theamount of said polyisocyanate in said composition, and a trimerizationcatalyst, said composition being essentially free of any mono- anddi-isocyanate monomers, and said composition being heat curable uponexposure to heat.

In yet another aspect, the present invention relates to a low volatileorganics-containing, one-component, moisture curable coating compositionhaving a viscosity as measured by ZAHN cup 2 of less than about 200seconds and consisting essentially of at least one polyisocyanateprepolymer which is the reaction product of a polyisocyanate with afluorine-containing, active hydrogen-containing compound alone or incombination with a fluorine-free active hydrogen-containing compound, asolvent in an amount of between 0% and 45% by weight based upon theamount of said composition, and a tertiary amine catalyst, saidcomposition being essentially free of any mono- and di-isocyanatemonomers, and said composition being moisture curable upon exposure toatmospheric or added moisture.

In still another aspect, the present invention relates to a low volatileorganics-containing, two-component, moisture curable coating compositionhaving a viscosity as measured by ZAHN cup 2 of less than about 200seconds and consisting essentially of at least one polyisocyanate, afluorine-containing, active hydrogen-containing compound alone or incombination with a fluorine-free active hydrogen-containing compound, asolvent in an amount of between 0% and 45% by weight based upon theamount of said polyisocyanate in said composition, and a tertiary aminecatalyst, said composition being essentially free of any volatile mono-and di-isocyanates, and said composition being moisture curable uponexposure to atmospheric or added moisture.

In yet another aspect, the present invention relates to a process forproviding a slippery coating on a substrate which comprises:

(a) contacting said substrate with a low volatile-organics,one-component, heat curable coating composition to form a coating onsaid substrate, said coating composition having a viscosity as measuredby ZAHN cup 2 of less than about 200 seconds and consisting essentiallyof at least one blocked polyisocyanate, a fluorine-containing activehydrogen-containing compound alone or in combination with afluorine-free active hydrogen-containing compound, a solvent in anamount of between 0% and 45% by weight based upon the amount of saidpolyisocyanate in said composition, and a trimerization catalyst, saidcomposition being essentially free of any mono- and di-isocyanatemonomers, and

(b) heating said coating to a curing temperature of between 120° F. and350° F. for a curing time of between about ten minutes and about sixhours in order to cure said coating by trimerizing at least someisocyanate groups of said polyisocyanate to provide a heat-cured coatingon said substrate,

said heat-cured coating being characterized by a contact angle ofgreater than 63 degrees.

In still another aspect, the present invention relates to a process forproviding a slippery coating on a substrate which comprises:

(a) contacting said substrate with a low volatile-organics,two-component, heat curable coating composition to form a coating onsaid substrate, said coating composition having a viscosity as measuredby ZAHN cup 2 of less than about 200 seconds and consisting essentiallyof at least one polyisocyanate, a fluorine-containing activehydrogen-containing compound alone or in combination with afluorine-free active hydrogen-containing compound, a solvent in anamount of between 0% and 45% by weight based upon the amount of saidpolyisocyanate in said composition, and a trimerization catalyst, saidcomposition being essentially free of any mono- and di-isocyanatemonomers, and

(b) heating said coating to a curing temperature of between 120° F. and350° F. for a curing time of between about ten minutes and about sixhours in order to cure said coating by trimerizing at least someisocyanate groups of said polyisocyanate to provide a heat-cured coatingon said substrate,

said heat-cured coating being characterized by a contact angle ofgreater than 63 degrees.

In still another aspect, the present invention relates to a process forproviding a slippery coating on a substrate which comprises:

(a) contacting said substrate with a low volatile organics-containing,one-component, moisture curable coating composition to form a coating onsaid substrate, said coating composition having a viscosity as measuredby ZAHN cup 2 of less than about 200 seconds and consisting essentiallyof at least one polyisocyanate prepolymer which is the reaction productof a polyisocyanate with a fluorine-containing, activehydrogen-containing compound alone or in combination with afluorine-free active hydrogen-containing compound, a solvent in anamount of between 0% and 45% by weight based upon the amount of saidcomposition, and a tertiary amine catalyst, said composition beingessentially free of any mono- and di-isocyanate monomers, and saidcomposition being moisture curable upon exposure to atmospheric or addedmoisture, and

(b) exposing said coating to atmospheric or added moisture to provide amoisture-cured coating on said substrate,

said moisture-cured coating being characterized by a contact angle ofgreater than 63 degrees.

In yet another aspect, the present invention relates to a process forproviding a slippery coating on a substrate which comprises:

(a) contacting said substrate with a low volatile organics-containing,two-component, moisture curable coating composition to form a coating onsaid substrate, said coating composition having a viscosity as measuredby ZAHN cup 2 of less than about 200 seconds and consisting essentiallyof at least one polyisocyanate, a fluorine-containing, activehydrogen-containing compound alone or in combination with afluorine-free active hydrogen-containing compound, a solvent in anamount of between 0% and 45% by weight based upon the amount of saidpolyisocyanate in said composition, and a tertiary amine catalyst, saidcomposition being essentially free of any volatile mono- anddi-isocyanates, and said composition being moisture curable uponexposure to atmospheric or added moisture, and

(b) exposing said coating to atmospheric or added moisture to provide amoisture-cured coating on said substrate,

said moisture-cured coating being characterized by a contact angle ofgreater than 63 degrees.

In still another aspect, the present invention relates to a coatedsubstrate produced by the above-described processes.

These and other aspects will become apparent upon reading the followingdetailed description of the invention.

DETAILED DESCRIPTION OF THE INVENTION

Without wishing to be bound to any particular theory, it has now beensurprisingly found in accordance with the present invention that the useof fluorine-containing monoahls in low VOC polyisocyanate-based coatingcompositions provides coatings characterized by enhances slipperinesscharacteristics on the outer surface thereof as measured by increasedcontact angle measurements relative to fluorine-free coatings, withoutcompromising the adhesion characteristics of the coating to theunderlying substrate to which the coating is bonded. This enhancedslipperiness result is believed by the present inventors to beattributable, at least in part, to an apparent tendency of the fluorineatoms in the coating to migrate to the outer surface of the coating,thereby increasing the contact angle values for the coating's outersurface.

The present invention provides so-called "one-component" and"two-component" coating compositions that have very low VOCs, aremoisture or heat curable, and are useful for coating a wide variety ofsubstrates. A heat-curable, one-component coating compositionadvantageously consists essentially of either a "blocked" or unblockedpolyisocyanate or polyisocyanate prepolymer, a fluorine-containingactive hydrogen-containing compound (also referred to herein as a"monoahl") or a combination of such fluorine-containing compound with afluorine-free monoahl, a trimerization catalyst to facilitate heatcuring of the composition, and an optional solvent. The moisturecurable, one-component composition typically employs a tertiary aminecatalyst to facilitate the moisture cure. Therefore, the moisturecurable, one-component coating composition consists essentially of apolyisocyanate prepolymer, which is the reaction product of apolyisocyanate with a fluorine-containing active hydrogen-containingcompound, or a combination of such fluorine-containing compound with afluorine-free monoahl, a tertiary amine catalyst to facilitate moisturecuring of the composition, and an optional solvent. The use of someamount of fluorine-free monoahl is advantageous since it aids inviscosity reduction for the one-component composition and provides arelatively inexpensive source of "bulk" for the coating composition. Thetwo-component composition, which can be either moisture curable or heatcurable will typically comprise an A-side and a B-side, wherein theA-side consists essentially of a polyisocyanate and an optional solvent,and the B-side consists essentially of a trimerization catalyst and/or atertiary amine catalyst and an active-hydrogen containing compoundselected from the group consisting of monoahls, polyols, imines (such asketimines and aldimines), oxazolidines, and combinations thereof. It ispreferable to use the two-component composition for applicationsrequiring the incorporation of pigment into the coating, since pigmentsnormally contain water which is not easily removed. The pigments thuscan be incorporated into the B-side which is not sensitive to moisture,in contrast to the moisture sensitivity of unblocked polyisocyanates ina one-component composition.

The coating composition of the present invention is a lowvolatile-organics (so-called "low VOC") coating composition having aviscosity as measured by ZAHN cup 2 of less than about 200 seconds andconsisting essentially of at least one polyisocyanate, a solvent in anamount of between 0% and 45% by weight based upon the amount of saidpolyisocyanate in said composition, and a trimerization and/or tertiaryamine catalyst, said composition being essentially free of any volatilemono- and di-isocyanates. The composition is curable by trimerization ofisocyanate groups of the polyisocyanate using a trimerization catalystupon exposure to heat at a temperature of between 120° F. and 350° F.for a curing time of between about ten minutes and about six hours, orby exposure to water at an ambient or elevated temperature for a curingtime of between about 10 minutes and about 6 hours in the presence of atertiary amine catalyst for promoting the water-isocyanate reaction.

Useful trimerization catalysts, for use in preparing heat curablecoating compositions, include the following: phosphines as described inU.S. Pat. No. 3,645,979; phosphorus acid triamides as described in U.S.Pat. No. 4,614,785; aminosilyl catalysts such as aminosilanes,diaminosilanes, silylureas, and silazanes as described in U.S. Pat. No.4,412,073; alkali alcoholates and phenolates, alkali carboxylates andalkali hydroxides as described in U.S. Pat. No. 2,978,449; tertiaryamines as described in U.S. Pat. No. 3,745,133 and U.S. Pat. No.3,981,829, aminimides as described in U.S. Pat. No. 4,067,830;quaternary ammonium carboxylates as described in U.S. Pat. No. 4,454,317and U.S. Pat. No. 4,801,663; quaternary ammonium hydroxides as describedin U.S. Pat. No. 4,324,879 and U.S. Pat. No. 5,124,427; Mannich bases,such as those based on nonylphenol, formaldehyde and dimethylamine asdescribed in U.S. Pat. No. 3,996,223 and U.S. Pat. No. 4,115,373; andthe like. The catalyst is suitably employed in an amount of betweenabout 0.01% and about 5%, based upon the weight of the coatingcomposition. Optionally, additional catalysts known to promote thereaction of isocyanates with other substituents, e.g. alcohols, may beutilized as desired, and such use is particularly advantageous intwo-component systems. Such additional catalysts, for example dibutyltindilaurate and stannous octoate, are suitably employed in an amount ofbetween about 0.01% and 5%, based upon the weight of the coatingcomposition.

In preparing moisture curable coating compositions, tertiary aminecatalysts are advantageously employed in order to promote thewater-isocyanate reaction. Useful tertiary amines include hydroxyl-freetertiary amines, as well as hydroxyl-containing tertiary aminecatalysts. Illustrative tertiary amine catalysts include the following:bis(N,N'-dimethylaminoethyl)ether, tris(dimethylaminopropyl)amine,N,N'-dimethylpiperazine, and pentamethyl-dipropylene triamine. Preferredtertiary amine catalysts are the hydroxyl-containing tertiary amines,including N,N'-dimethylethanolamine, N,N-dimethylamino-ethoxyethanol,N,N'-dimethylaminoethyl-N-methylethanolamine,N,N-dimethyl-N',N'-2-hydroxypropyl-1,3-propylene diamine,N,N,N'-trimethyl-N'-hydroxylethyl-bis(amino ethyl)ether,N,N-bis(3-dimethylaminopropyl)amino-2-propanol. The tertiary aminecatalyst is suitably employed in an amount of between about 0.1% andabout 5%, based upon the weight of the coating composition. Optionally,additional catalysts which promote polymer-forming reactions, such asthe above-described dibutyltin dilaurate and stannous octoate catalystscan be employed. Such additional catalysts are suitably employed in thecoating composition in an amount of between about 0.01% and about 1% byweight, based upon the weight of the coating composition.

As a measure of the viscosity of the coating composition employed in thepresent invention, the ZAHN cup 2 test is performed in accordance withASTM D4212-88. Briefly, the ZAHN cup 2 test is performed by dipping ameasured cup having a bottom hole into the test composition, followed byremoval of the cup and measurement of the amount of time in secondsuntil a break occurs in the flow stream of test composition passingthrough the bottom hole. For purposes of comparison, the viscosities asmeasured by Zahn cup No. 2 can be converted to approximate kinematicviscosities, if desired, by a computation using the following equation:

    viscosity (in centistokes)=2.93(t)-500/(t)

where t is the viscosity in seconds as measured by the Zahn cup No. 2test regimen.

The polyisocyanates useful in the process of the present invention arethose containing one or more of the following: biuret groups,isocyanurate groups (such as cyclotrimerized isocyanate groups),uretidione groups, allophanate groups, urethane groups and combinationsthereof. The polyisocyanate suitably has an average functionality of atleast 2, preferably between 2.5 and 6, most preferably between 3 and 6.Suitable polyisocyanates include aliphatic polyisocyanates, aromaticpolyisocyanates, and combinations thereof, but preferably at least someamount of an aliphatic polyisocyanate is employed in the process of thepresent invention. Polyisocyanates containing aliphatically and/orcycloaliphatically bound isocyanate groups are preferred for theproduction of light-stable coatings.

In preparing heat curable coating compositions, blocking agents aresuitably employed to block one or more of the isocyanate groups on thepolyisocyanate if desired. Heat unblocking of the polyisocyanate is theneffected at the desired temperature as a prelude to the coatingformation. Suitable blocking agents include those well-known in the artsuch as, for example, aromatic alcohols such as phenol, cresols,trimethyl phenols and tert-butyl phenols; tertiary alcohols such astert-butanol, tert-amyl alcohol, and dimethyl phenyl carbinol; compoundswhich readily form enols such as ethyl acetoacetate, acetyl acetone andmalonic acid diethyl ester; secondary aliphatic and aromatic amines suchas dibutyl amine, N-methyl aniline, the N-methyl toluidines, N-phenyltoluidine and N-phenyl xylidine; imides such as succinimide; lactamssuch as e-caprolactam and d-valerolactam; oximes such as butanone oximeand cyclohexanone oxime; mercaptans, such as methyl mercaptan, ethylmercaptan, butyl mercaptan, 2-mercapto-benzothiazole, alpha-naphthylmercaptan and dodecyl mercaptan; triazoles such as 1-H-1,2,4-triazole;and pyrazoles such as 3,5-dimethylpyrazole, 3-methylpyrazole,4-nitro-3,5-dimethylpyrazole, and 4-bromo-3,5-dimethylpyrazole.

The polyisocyanates are prepared by the known modification of simpleorganic diisocyanates, typically resulting in the formation of biuret,uretidione, allophanate, urethane or isocyanurate groups, or thesimultaneous formation of isocyanurate and uretidione groups. Any excessof unmodified monomeric starting isocyanate still present after themodification reaction is suitably removed in a known manner, such asdistillation, to provide a polyisocyanate that is essentially free ofvolatile diisocyanate. The term "essentially free of volatilediisocyanate" as used herein is intended to designate that thepolyisocyanate contains no greater than 0.7%, preferably no greater than0.5%, most preferably no greater than 0.2%, by weight of volatilediisocyanate based upon the weight of the polyisocyanate.

Diisocyanates suitable for use in the preparation of the polyisocyanatesinclude, for example, 2,4- and/or 2,6 diisocyanatotoluene,4,4'-diisocyanato-dicyclohexylmethane, hexamethylene diisocyanate("HDI"),and 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane("IPDI"), 1,4-butanediisocyanate, 1-methyl-2,4-diisocyanatocyclohexane,1-methyl-2,6-diisocyanatocyclohexane, 4,4'-methylene-bis(cyclohexylisocyanate), 2-methyl-1,5-diisocyanatopentane,2-ethyl-1,4-diisocyanatobutane,2,4,4-trimethylhexamethylene-1,6-diisocyanate,a,a'-diisocyanato-1,3-dimethylbenzene,a,a'-diisocyanato-1,3-dimethylcyclohexane,a,a'-diisocyanato-1,4-dimethylbenzene,a,a'-diisocyanato-1,4-dimethylcyclohexane, 1,3-diisocyanatocyclohexane,1,4-diisocyanatocyclohexane wherein "a" denotes "alpha". Thepolyisocyanates may also be suitably prepared from mixtures of these, orother, diisocyanates, and mixtures of a polyisocyanate with anon-volatile isocyanate, such as octadecyl-isocyanate, are also suitablefor use within the scope of the present invention. Preferably, aliphaticor cycloaliphatic diisocyanates are utilized as starting materials forpreparing the polyisocyanates. HDI and IPDI are the most preferredstarting materials for the preparation of polyisocyanates. Thus, mostpreferred polyisocyanates include tris-(isocyanatohexyl)-biuret,tris-(isocyanatohexyl)-isocyanurate, cyclodimerized HDI and mixturesthereof, as well as mixtures of these oligomeric polyisocyanates withtheir higher homologues. Trimerized HDI is available under the trademarkof LUXATE, a product of Olin Corporation, as well as under the trademarkDESMODUR, a product of Miles Inc.

The coating compositions of the present invention must contain at leastsome amount of fluorine-containing active hydrogen-containing compound,preferably an amount of between about 0.05 and about 10% weight percent,based upon the weight of the coating composition. The coatingcomposition may optionally contain fluorine-free monoahl(s) and/orpolyol(s), and one or more of these components may be desirable in orderto avoid any unnecessary extra expense associated with using allfluorine-containing active hydrogen-containing compounds while alsoavoiding shrinkage problems during curing of the coating composition onthe desired substrate, the latter problem being one that sometimesoccurs when no (or too small an amount of) active hydrogen-containingcompound is employed in the coating composition. In any event, the totalamount of active hydrogen-containing compound is advantageously betweenabout 0.05 and about 10% weight percent based upon the weight of thecoating composition.

The active hydrogen-containing compound useful in the process of thepresent invention is suitably selected from the group consisting ofmonoahls, polyols, imines (such as ketimines and aldimines),oxazolidines, and combinations thereof, preferably having a weightaverage molecular weight of between about 50 and about 10,000, morepreferably between about 100 and about 5,000, most preferably about 200and about 2,000.

The term "monoahl" is intended to designate compounds having only oneactive hydrogen group. An active hydrogen group is a group which has ahydrogen atom which, because of its position in the molecule, displaysactivity according to the Zerewitnoff test described by Woller in theJournal of American Chemical Society, Vol. 49, page 3181(1927).Illustrative of such active hydrogen groups are --OH, --NH--, --COOH,--SH and --CONH--. Typical monoahls suitable for this invention includemonoalcohols, monoamines, thiols, amides and imines. Suitablemonoalcohols are the aliphatic or cycloaliphatic alcohols, optionallycontaining ester or ether linkages. Preferred monoahls are monohydricpolyethers and monohydric polyesters. Monohydric polyethers are preparedby the polymerization of alkylene oxides with alcohols. Alcohols whichmay be employed in the polymerization include C1-C30(cyclo)aliphaticstraight- or branched-chain alcohols, such as methanol, ethanol,propanol, isopropanol, butanol, hexanol, cyclohexanol, and the like, andmixtures thereof. Illustrative alkylene oxides used in thepolymerization include ethylene oxide, propylene oxide, butylene oxide,and the like. Monohydric polyesters are most readily prepared by thepolymerization of lactones such as butyrolactone, valerolactone,caprolactone, and the like reacted with alcohols, such as the alcoholsdescribed above. Suitable alcohols include the alcohols described abovefor polymerization with alkylene oxides.

Suitable monoamines are aliphatic or cycloaliphatic, primary orsecondary amines. Preferred amines are poly(alkyleneoxy)alkylamines.

Polyols suitable for the present invention include polyether polyols andpolyester polyols. The preferred polyols useful in the present inventionhave a functionality of about 2 in order to prevent the formation ofvery high molecular weight polyurethane prepolymers which result incoating viscosities higher than desired for ready application. Thepolyether polyols are prepared by polymerization of alkylene oxides withwater, polyhydric alcohols with two to eight hydroxyl groups, or amines.Polyester polyols include the condensation products of polycarboxylicacids with polyhydric alcohols.

In preparing the polyisocyanate prepolymers useful in the presentinvention, and in utilizing the polyisocyanates in both theone-component and two-component systems of the present invention, theratio of NCO equivalents in the polyisocyanate to the OH equivalents inthe active hydrogen-containing compound can vary over a wide range ofbetween about 2:1 and about 10,000:1, preferably between about 2.5:1 andabout 2,000:1, most preferably between about 3:1 and about 2,000:1.

The coating compositions employed in the process of the presentinvention suitably contain small quantities of isocyanate-inert solventsin amounts of between 0% and 45% by weight, based upon the weight of thecoating composition. It is preferred to minimize the amount of solventutilized in the coating compositions of the present invention in orderto minimize the VOC of the coating composition itself. However, someamount of solvent may be required in order to provide a desired lowviscosity for the coating composition of less than about 200 seconds asmeasured by Zahn cup #2. Suitable solvents include toluene, xylene,butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methylamylketone, ethylethoxy propionate, ethoxyethylacetate, an aromatichydrocarbon mixture having a boiling point of 152-174° C., combinationsthereof, and the like. Other optional additives are suitably employed,if desired, such as, for example, uv stabilizers; leveling agents;flow-aids; pigments, such as titanium dioxide; plasticizers; and/orother resins.

The coating compositions made in accordance with the process of thepresent invention are suitable for use in the production of clear orpigmented coatings, and may be applied to a desired substrate byconventional methods, such as spread coating, roller application orspraying. Because of the low viscosity of the compositions of thepresent invention, they are especially suitable for application byconventional spray techniques. The coating thickness on the substratecan vary over a wide range, although a dry film coating thickness ofbetween about 0.01 and 0.5 millimeters is preferred.

Substrates for the coating useful in the present invention are suitablyselected from a wide range of materials such as other plastics, such aspolyethylene or polystyrene, wood and paper substrates, and metalsubstrates, such as sheet steel or aluminum.

The coating compositions of the present invention are stable in storagewhen heat and moisture are excluded and they harden under the influenceof heat and/or moisture to form coatings. As stated above, whenhardening or curing of the coatings on the substrate in accordance withthe invention is carried out by exposure to heat, the temperatureemployed is between 120° F. and 350° F. for a curing time of betweenabout ten minutes and about six hours. When curing is effected byexposure to moisture, an ambient or elevated temperature is suitablyemployed using a curing time of between about ten minutes and about sixhours.

The coatings of the present invention are suitable for use in theproduction of automotive clear coatings or undercoats, floor coveringcoatings, wall coatings, transportation coatings, maintenance coatings,and the like, or any other application where a low VOC coatingcomposition is desired for use on a substrate. The "slippery" coatingsproduced in accordance with the present invention provide particularadvantages in coatings applications requiring anti-graffiticharacteristics, acid etch resistance, and easy dirt removal, in eitherindoor or outdoor applications. These slippery coatings generallyprovide a contact angle for deionized water of greater than 63 degrees,preferably greater than 80 degrees, more preferably greater than 90degrees.

While the invention has been described above with reference to specificembodiments thereof, it is apparent that many changes, modifications andvariations can be made without departing from the inventive conceptdisclosed herein. Accordingly, it is intended to embrace all suchchanges, modifications and variations that fall within the spirit andbroad scope of the appended claims. All patent applications, patents andother publications cited herein are incorporated by reference in theirentirety.

The following examples are intended to illustrate, but in no way limitthe scope of, the present invention.

EXAMPLES

The following products were utilized in the examples given hereinbelow:

Monoahl A is an ethoxylated/propoxylated alcohol initiated withtrifluoroethanol and having an average molecular weight of about 505.

Monoahl B is a mixture of ethoxylated/propoxylated C6-C10 alcoholshaving an average molecular weight of about 530.

Monoahl C is a mixture of perfluoroalkylsulfonamido alcohols sold underthe tradename of FC-10 Fluorad Brand Fluorochemical Alcohol by 3Mequivalent weight 570-590 (56.5% Fluorine).

Monoahl D is a fluorinated monoether alcohol sold under the tradename ofZonyl FSO 100 Fluorosurfactant by DuPont, equivalent weight 720-740.

Polyisocyanate A is a trimerized 1.6 hexamethylene diisocyanate (%NCO=21-23).

Polyisocyanate B is a trimerized 1,6-hexamethylene diisocyanate blockedwith 3,5-dimethylpyrazole, as a 75% solution in n-butyl acetate andAromatic 100 from Exxon (% NCO=9.6-10.5).

Catalyst A is 2-((2-(2-(dimethylamino)ethoxy) ethyl)methylamino)ethanoland sold under the tradename of Texacat ZF-10 by Texaco.

Catalyst B is a 5% solution of dibutyltin dilaurate in toluene.

Flow-aid A is an acrylic flow and leveling agent sold as a 60% solidssolution in xylene under the tradename Coroc A-620-A2 by FreemanPolymers.

Preparation of Coating Compositions-Examples and Comparisons Example 1

Preparation of one-component moisture cured system

A 500-ml, 3-necked flask was charged with 40 g of Monoahl A, 3.0 g ofCatalyst A, 0.4 g of Catalyst B, 0.8 g of Flow-aid A, 42.5 g of butylacetate (BA), and 42.5 g of ethylethoxypropionate (EEP). The flask wasplaced under positive nitrogen pressure while 163 g of Polyisocyanate Awas added to the mixture. The resulting mixture was then heated to 80°C. and was stirred at that temperature for 3 hours to complete thereaction. The resultant coating composition had a viscosity of 31seconds by No. 2 Zahn cup at 20° C.

Example 2 Preparation of one-component moisture cured system

A 500-ml, 3-necked flask was charged with 20 g of Monoahl B, 10 g offluoroethanol, 4.4 g of Catalyst A, 0.6 g of Catalyst B, 1.2 g ofFlow-aid A, 57 g of butyl acetate (BA), and 57 g ofethylethoxypropionate (EEP). The flask was placed under positivenitrogen pressure while 267 g of Polyisocyanate A was added to themixture. The resulting mixture was then heated to 60° C. and was stirredat that temperature for 3 hours to complete the reaction. The resultantcoating composition had a viscosity of 37 seconds by No. 2 Zahn cup at20° C.

Example 3 Preparation of one-component moisture cured system

A 500-ml, 3 necked flask was charged with 8 g of1,1-dihydroheptafluorobutanol, 1.3 g of Catalyst A, 0.17 g of CatalystB, 0.35 g of Flow-aid A, 17 g of butyl acetate (BA), and 17 g ofethylethoxypropionate (EEP). The flask was placed under positivenitrogen pressure while 80 g of Polyisocyanate A was added to themixture. The resulting mixture was then heated to 80° C. and was stirredat that temperature for 3 hours to complete the reaction. The resultantcoating composition had a viscosity of 31 seconds by No. 2 Zahn cup at20° C.

Example 4 Preparation of one-component moisture cured system

A 500-ml, 3-necked flask was charged with 24 g of Monoahl C, 1.5 g ofCatalyst A, 0.2 g of Catalyst B, 0.41 g of Flow-aid A, 20 g of butylacetate (BA), and 20 g of ethylethoxypropionate (EEP). The flask wasplaced under positive nitrogen pressure while 80 g of Polyisocyanate Awas added to the mixture. The resulting mixture was then heated to 80°C. and was stirred at that temperature for 3 hours to complete thereaction. The resultant coating composition had a viscosity of 32seconds by No. 2 Zahn cup at 20° C.

Example 5 Preparation of one-component moisture cured system

A 500-ml, 3-necked flask was charged with 11.9 g of Monoahl C, 10.8 g ofMonoahl B, 1.5 g of Catalyst A, 0.2 g of Catalyst B, 0.4 g of Flow-aidA, 20 g of butyl acetate (BA), and 20 g of ethylethoxypropionate (EEP).The flask was placed under positive nitrogen pressure while 80 g ofPolyisocyanate A was added to the mixture. The resulting mixture wasthen heated to 80° C. and was stirred at that temperature for 3 hours tocomplete the reaction. The resultant coating composition had a viscosityof 32 seconds by No. 2 Zahn cup at 20° C.

Example 6 Preparation of one-component moisture cured system

A 500-ml, 3-necked flask was charged with 6.0 g of Monoahl C, 15.8 g ofMonoahl B, 1.5 g of Catalyst A, 0.2 g of Catalyst B, 0.4 g of Flow-aidA, 20 g of butyl acetate (BA), and 20 g of ethylethoxypropionate (EEP).The flask was placed under positive nitrogen pressure while 80 g ofPolyisocyanate A was added to the mixture. The resulting mixture wasthen heated to 80° C. and was stirred at that temperature for 3 hours tocomplete the reaction. The resultant coating composition had a viscosityof 31 seconds by No. 2 Zahn cup at 20° C.

Example 7 Preparation of one-component moisture cured system

A 500-ml, 3-necked flask was charged with 30 g of Monoahl D, 1.6 g ofCatalyst A, 0.22 g of Catalyst B, 0.44 g of Flow-aid A, 21 g of butylacetate (BA), and 21 g of ethylethoxypropionate (EEP). The flask wasplaced under positive nitrogen pressure while 80 g of Polyisocyanate Awas added to the mixture. The resulting mixture was then heated to 80°C. and was stirred at that temperature for 3 hours to complete thereaction. The resultant coating composition had a viscosity of 38seconds by No. 2 Zahn cup at 20° C.

Example 8 Preparation of two-component moisture cured system

A 16-oz, wide-mouth bottle was charged with 52 g ofethylethoxypropionate (EEP), 1.5 g of Catalyst A, 0.2 g of Catalyst B,0.4 g of Flow-aid A, 1.0 g of Mono-ol C, 20 g of Monoahl B, and 80 g ofPolyisocyanate A. The resulting mixture was stirred with a spatula toproduce the coating composition as a clear, homogeneous solution usedimmediately to prepare coatings.

Example 9 Preparation of two-component moisture cured system

A 16-oz, wide-mouth bottle was charged with 52 g ofethylethoxypropionate (EEP), 1.5 g of Catalyst A, 0.2 g of Catalyst B,0.4 g of Flow-aid A, 3.0 g of Mono-ol C, 20 g of Monoahl B, and 80 g ofPolyisocyanate A. The resulting mixture was stirred with a spatula toproduce the coating composition as a clear, homogeneous solution, usedimmediately after mixing to prepare coatings.

Comparative Example 1 Preparation of two-component moisture cured systemwithout added fluorocompound

A 16-oz, wide-mouth bottle was charged with 52 g ofethylethoxypropionate (EEP), 1.5 g of Catalyst A, 0.2 g of Catalyst B,0.4 g of Flow-aid A, 20 g of Monoahl B, and 80 g of Polyisocyanate A.The resulting mixture was stirred with a spatula to produce the coatingcomposition as a clear, homogeneous solution, used immediately aftermixing to prepare coatings.

Example 10 Preparation of two-component heat cured system

A 500-ml, 3-necked flask was charged with 3.7 g of Monoahl C, 7.4 g ofMonoahl B, 0.44 g of Catalyst B. The flask was placed under positivenitrogen pressure while 29.59 g of Polyisocyanate A was added to themixture. The resulting mixture was then heated to 80° C. and was stirredat that temperature for 3 hours to complete the reaction. To the abovesolution were added, 7.8 g of toluene, 11.8 g of ethyl3-ethoxypropionate and 0.39 g of potassium trifluoroacetate (20%solution in triethylene glycol monomethyl ether). The obtained solutionwas then immediately used to prepare coatings.

Example 11 Preparation of two-component heat cured system

A 500-ml, 3-necked flask was charged with 3.9 g of Monoahl C, 7.83 g ofMonoahl B, 0.47 g of Catalyst B. The flask was placed under positivenitrogen pressure while 31.33 g of Polyisocyanate A was added to themixture. The resulting mixture was then heated to 80° C. and was stirredat that temperature for 3 hours to complete the reaction. To the abovesolution were added, 7.8 g of toluene, 11.8 g of ethyl3-ethoxypropionate and 0.39 g of potassium trifluoroacetate (20% intriethylene glycol monomethyl ether). The obtained solution was thenimmediately used to prepare coatings.

Example 12 Preparation of two-component heat cured system

A 500-ml, 3-necked flask was charged with 0.04 g of Monoahl C, 7.88 g ofMonoahl B, 0.47 g of Catalyst B. The flask was placed under positivenitrogen pressure while 31.52 g of Polyisocyanate A was added to themixture. The resulting mixture was then heated to 80° C. and was stirredat that temperature for 3 hours to complete the reaction. To the abovesolution were added, 7.8 of toluene, 11.8 g of ethyl 3-ethoxypropionate,and 0.39 g of potassium trifluoroacetate (20% solution in triethyleneglycol monomethyl ether). The obtained solution was then immediatelyused to prepare coatings.

Preparation of one-component heat cured system

A 500-ml, 3-necked flask was charged with 0.39 g of Monoahl C, 7.83 g ofMonoahl B, 0.47 g of Catalyst B. The flask was placed under positivenitrogen pressure while 62 g of Polyisocyanate B was added to themixture. To the above solution were added, 7.8 of toluene, 11.8 g ofethyl 3-ethoxypropionate, and 0.39 g of potassium trifluoroacetate (20%solution in triethylene glycol monomethyl ether). The resulting mixturewas stirred at room temperature for 15 minutes. The obtained solution ofa one-component system was used to prepare coatings (coating example27).

Comparative Example 2 Preparation of two-component moisture cured systemwithout added fluorocompound

A 500-ml, 3-necked flask was charged with 7.88 g of Monoahl B, 0.47 g ofCatalyst B. The flask was placed under positive nitrogen pressure while31.54 g of Polyisocyanate A was added to the mixture. The resultingmixture was then heated to 80° C. and was stirred at that temperaturefor 3 hours to complete the reaction. To the above solution were added,7.8 g of toluene, and 11.8 g of ethyl 3-ethoxypropionate, and 0.39 g ofpotassium trifluoroacetate (20% in triethylene glycol monomethyl ether).The obtained solution was then immediately used to prepare coatings.

Testing of Coatings Made Using the Above Compositions Examples 14-23

The coating compositions prepared in Examples 1-9 and ComparativeExample 1 were sprayed at 45 psi using a conventional spray gun (model#DH6500 from Binks Mfg. Co.) on cold-rolled steel panels. A smallportion of the coating composition was used to coat a glass strip whichwas placed in a BK Drying Recorder (Paul N. Gardner Company, Inc.) todetermine the drying time. The recorder uses a tracking needle todetermine the solvent evaporation time, the gel time and the surface-drytime. The drying time determinations were made at 20° C. and 50%relative humidity.

The coated test panels were allowed to cure at ambient temperature andhumidity conditions for two weeks before testing for appearance,mechanical properties, and chemical resistance. Pencil hardness wasdetermined according to ASTM D3363-92a. The conical mandrel bend testswere performed using a one-eighth inch tester from BYK-Gardner, Inc.according to ASTM D522-92. Direct and reverse impact values weredetermined according to ASTM D2794-92 using a variable height impacttester from BYK-Gardner, Inc. Gloss was determined using amicro-TRZ-gloss, multi-angle glossmeter from BYK-Gardner, Inc.Cross-hatch adhesion was determined using a cross-hatch cutter fromBYK-Gardner according to ASTM D3359-92 a. Chemical resistance wasdetermined according to ASTM D1308-87. Contact angles for the coatingswith deionized water were measured using a Rame-Hart 100-00-115 ContactAngle Analyzer.

Examples 24-28

The coating compositions prepared in Examples 10-13 and ComparativeExample 2 were applied to cold-rolled steel panels by drawing down afilm of about 2 mils thickness. The coated test panels were cured in anoven held at 147-154° C. Contact angles for the coatings with deionizedwater were measured using a Rame-Hart 100-00-115 Contact Angle Analyzer.

The results of the various physical property test measurements for thecoatings of Examples 1 through 26 are given in Tables 1 and 2 presentedhereinbelow. These results demonstrate that improved results, in termsof increased contact angle values, are provided for the coatings ofExamples 1-12 (ranging from 64 to 109) made using coating compositionsusing a fluoro-containing monoalcohol, as compared to the valuesobtained for Comparative Examples 1 and 2 (values of 55 and 61 degrees,respectively) measured on coatings made using fluorine-free monols.

Although most of the other coatings properties shown in Table 1 areacceptable for a wide variety of applications, those showing a poorresult in one or two properties would be suitably utilized inapplications not requiring those properties.

                                      TABLE I    __________________________________________________________________________    Moisture Cure at Room Temperature    __________________________________________________________________________                Solvent                       Gel Surface              Direct                                                    Reverse         Coating                Evaporation                       Time                           Dry  Thickness                                      Pencil                                           Mandrel                                                Impact                                                    Impact    Example         Composition                (min)  (min)                           (min)                                (mils)                                      Hardness                                           Bend (in/lb)                                                    (in/lb)    __________________________________________________________________________    14   Example 1                20     50  150  1.5   4    Pass 160 160    15   Example 2                15     30  120  3     4    Pass 160 160    16   Example 3                50     80  225  2     4    Pass 160 140    17   Example 4                15     30   60  1.7   4    Pass 160 160    18   Example 5                15     30  120  NT    NT   NT   NT  NT    19   Example 6                NT     NT  NT   NT    NT   NT   NT  NT    20   Example 7                20     80  150  1.7   4    Pass 160 160    21   Example 8                NT     NT  NT   NT    NT   NT   NT  NT    22   Example 9                NT     NT  NT   NT    NT   NT   NT  NT    23   Comp. Ex. 1                NT     NT  NT   NT    NT   NT   NT  NT    __________________________________________________________________________                               Chemical                                    Resistance         Gloss             Gloss Crosshatch                         NaOH  HCl  CH.sub.3 COOH                                          MEK Xylene                                                    Contact    Example         (60°)             (20°)                   Adhesion                         (10%) (10%)                                    (10%) RUB RUB   Angle    __________________________________________________________________________    14   96%  94%  Pass  Pass  Fail Fail  Pass                                              Pass  67°    15   94% 107%  Pass  Pass  Pass Pass  Pass                                              Pass  68°    16   100%             115%  Pass  Pass  Pass Pass  Pass                                              Pass  74°    17   108%              90%  Pass  Pass  Pass Pass  Pass                                              Pass  98°    18   NT  NT    NT    NT    NT   NT    NT  NT    94°    19   NT  NT    NT    NT    NT   NT    NT  NT    93°    20   96% 106%  Pass  Pass  Fail Fail  Pass                                              Pass  82°    21   NT  NT    NT    NT    NT   NT    NT  NT    64°    22   NT  NT    NT    NT    NT   NT    NT  NT    103°    23   NT  NT    NT    NT    NT   NT    NT  NT    55°    __________________________________________________________________________     "NT" denotes not tested.

                                      TABLE II    __________________________________________________________________________    Heat Cure at 147-154° C.    __________________________________________________________________________                Solvent                       Surface              Direct                                                Reverse         Coating                Evaporation                       Dry  Thickness                                  Pencil                                       Mandrel                                            Impact                                                Impact    Example         Composition                (min)  (min)                            (mils)                                  Hardness                                       Bend (in/lb)                                                (in/lb)    __________________________________________________________________________    24   Example 10                5      30   NT    4    Pass 160 160    25   Example 11                5      30   NT    4    Pass 160 160    26   Example 12                5      30   NT    4    Pass 160 160    27   Example 13                5      90   1.8   4    Pass 160 160    28   Comp. Ex. 25                5      30   NT    4    Pass 160 160    __________________________________________________________________________                            Chemical                                 Resistance         Gloss             Gloss                  Crosshatch                        NaOH                            HCl  CH.sub.3 COOH                                       MEK  Xylene                                                Contact    Example         (60°)             (20°)                  Adhesion                        (10%)                            (10%)                                 (10%) RUB  RUB Angle    __________________________________________________________________________    24   NT  NT   Pass  Pass                            Pass Pass  NT   NT  109°    25   NT  NT   Pass  Pass                            Pass Pass  NT   NT  98°    26   NT  NT   Pass  Pass                            Pass Pass  NT   NT  93°    27   103 83   Pass  Pass                            Fail Pass  Pass Pass                                                70°    28   NT  NT   Pass  Pass                            Pass Pass  NT   NT  61°    __________________________________________________________________________     "NT" denotes not tested.

What is claimed is:
 1. A process for providing a slippery coating on asubstrate which comprises:(a) contacting said substrate with a lowvolatile-organics, one-component, heat curable coating composition toform a coating on said substrate, said coating composition having aviscosity as measured by ZAHN cup 2 of less than about 200 seconds andconsisting essentially of at least one blocked polyisocyanate, afluorine-containing monoahl alone or in combination with a fluorine-freeactive hydrogen-containing compound, a solvent in an amount of between0% and 45% by weight based upon the amount of said polyisocyanate insaid composition, and a trimerization catalyst, said composition beingessentially free of any mono- and di-isocyanate monomers, and (b)heating said coating to a curing temperature of between 120° F. and 350°F. for a curing time of between about ten minutes and about six hours inorder to cure said coating by trimerizing at least some isocyanategroups of said polyisocyanate to provide a heat-cured coating on saidsubstrate,said heat-cured coating being characterized by a contact angleof greater than 63 degrees.
 2. A process for providing a slipperycoating on a substrate which comprises:(a) contacting said substratewith a low volatile-organics, two-component, heat curable coatingcomposition to form a coating on said substrate, said coatingcomposition having a viscosity as measured by ZAHN cup 2 of less thanabout 200 seconds and consisting essentially of at least onepolyisocyanate, a fluorine-containing monoahl alone or in combinationwith a fluorine-free active hydrogen-containing compound, a solvent inan amount of between 0% and 45% by weight based upon the amount of saidpolyisocyanate in said composition, and a trimerization catalyst, saidcomposition being essentially free of any mono- and di-isocyanatemonomers, and (b) heating said coating to a curing temperature ofbetween 120° F. and 350° F. for a curing time of between about tenminutes and about six hours in order to cure said coating by trimerizingat least some isocyanate groups of said polyisocyanate to provide aheat-cured coating on said substrate,said heat-cured coating beingcharacterized by a contact angle of greater than 63 degrees.
 3. Aprocess for providing a slippery coating on a substrate whichcomprises:(a) contacting said substrate with a low volatileorganics-containing, one-component, moisture curable coating compositionto form a coating on said substrate, said coating composition having aviscosity as measured by ZAHN cup 2 of less than about 200 seconds andconsisting essentially of at least one polyisocyanate prepolymer whichis the reaction product of a polyisocyanate with a fluorine-containing,monoahl alone or in combination with a fluorine-free activehydrogen-containing compound, a solvent in an amount of between 0% and45% by weight based upon the amount of said composition, and a tertiaryamine catalyst, said composition being essentially free of any mono- anddi-isocyanate monomers, and said composition being moisture curable uponexposure to atmospheric or added moisture, and (b) exposing said coatingto atmospheric or added moisture to provide a moisture-cured coating onsaid substrate,said moisture-cured coating being characterized by acontact angle for deionized water on the coating of greater than 63degrees.
 4. A process for providing a slippery coating on a substratewhich comprises:(a) contacting said substrate with a low volatileorganics-containing, two-component, moisture curable coating compositionto form a coating on said substrate, said coating composition having aviscosity as measured by ZAHN cup 2 of less than about 200 seconds andconsisting essentially of at least one polyisocyanate, afluorine-containing, monoahl alone or in combination with afluorine-free active hydrogen-containing compound, a solvent in anamount of between 0% and 45% by weight based upon the amount of saidpolyisocyanate in said composition, and a tertiary amine catalyst, saidcomposition being essentially free of any volatile mono- anddi-isocyanates, and said composition being moisture curable uponexposure to atmospheric or added moisture, and (b) exposing said coatingto atmospheric or added moisture to provide a moisture-cured coating onsaid substrate,said moisture-cured coating being characterized by acontact angle of greater than 63 degrees.
 5. The process of any ofclaims 1 through 4 wherein said fluorine-containing monoahl is selectedfrom the group consisting of monoahls, polyols, imines and combinationsthereof.
 6. The process of any of claims 1 through 4 wherein saidsolvent is selected from the group consisting of toluene, xylene, butylacetate, methyl ethyl ketone, methyl isobutyl ketone, methylamyl ketone,ethoxyethylacetate, ethylethoxy propionate an aromatic hydrocarbonmixture having a boiling point of 152-174° C., and combinations thereof.7. The process of any of claims 1 through 4 wherein said polyisocyanatehas an average functionality of least
 2. 8. The process of any of claims1 through 4 wherein said fluorine-free active hydrogen-containingcompound is selected from the group consisting of monoahls, polyols,imines and combinations thereof.
 9. The process of any of claims 1through 4 wherein said polyisocyanate contains a moiety selected fromthe group consisting of biuret, uretidione, isocyanurate, urethane,allophanate, and combinations thereof.
 10. The process of any of claims1 through 4 wherein said polyisocyanate is selected from the groupconsisting of tris-(isocyanatohexyl)-biuret,tris-(isocyanatohexyl)-isocyanurate, cyclodimerized hexamethylenediisocyanate, and combinations thereof.
 11. A coated substrate producedby the process of any of claims 1 through 4 and characterized by afluoro-containing coating on said coated substrate.